Process for the manufacture of butenediol

ABSTRACT

Butenediol is obtained by reacting butadiene with water and oxygen in the presence of an iron catalyst and preferably in the presence of carbon dioxide or sulphur dioxide.

This invention relates to the manufacture of butenediols and more particularly to the manufacture of 2-butene-1, 4-diol.

It is known from German OLS No. 2607039 to react an aliphatic olefine, particularly a mono olefine, containing 2 to 4 carbon atoms in an aqueous medium with copper or iron cations and bromine containing anions, optionally in the presence of molecular oxygen so as to produce vicinal glycols such as ethylene glycol and 1 2,-propylene glycol. We have now found that when the olefine is butadiene the product of the reaction includes 2-butene-1, 4-diol and that the reaction may be carried out in the presence of anions other than bromine containing anions.

Thus according to our invention a process for the manufacture of 2-butene-1, 4-diol comprises reacting butadiene with water and oxygen in the presence of an iron catalyst.

The reaction is preferably effected in the presence of carbon dioxide or sulphur dioxide and may be effected in either the liquid or the vapour phase.

At least 1 mole of water is used per mole of butadiene, but an excess may be used, for example up to 10 moles/mole.

The oxygen may be molecular oxygen as such or may be a molecular oxygen-containing gas consisting of a mixture of oxygen with another gas which does not interfere with the reaction, for example nitrogen or argon. Air may be used, as may mixtures of oxygen and nitrogen with a higher or lower oxygen content than that of air.

The carbon dioxide or sulphur dioxide, when used, acts as a promoter and need not be used in equimolar amounts compared with that of the butadiene. Amounts of from 0.01 to 0.5 mols of carbon dioxide or sulphur dioxide per mole of butadiene are convenient, although larger amounts are not deleterious and are not excluded.

The catalyst may be iron itself or an iron compound or a mixture of iron and an iron compound. The iron compound is particularly a salt, for example an inorganic salt such as a halide, for example chloride, bromide or iodide, or an organic acid salt, especially a carboxylate and particularly a salt of an aliphatic carboxylic acid having up to 20 preferably up to 6 carbon atoms. The iron in the iron compound may be in the ferrous or ferric state. Among the iron compounds which may be used in the process are included ferrous chloride, ferrous bromide, ferrous and ferric acetate, ferric glycollate, ferric lactate, ferric acetyl-acetonate and ferric stearate.

It is also advantageous to carry out the reaction in the presence of lithium hydroxide.

When the reaction is effected in the liquid phase it is conveniently carried out in the presence of a solvent. The solvent is preferably water-miscible. Suitable solvents are, for example, lower (e.g. C₁ to C₆) aliphatic alcohols, lower (e.g. C₁ to C₆) aliphatic ketones and lower (e.g. C₁ to C₆) alkyl cyanides, for example ethanol, n-propanol, isopropanol, butanols, especially t-butanol, butenediol, acetone, methyl ethyl ketone, methyl isobutyl ketone and acetonitrile. Compounds may be added which may assist the solubility of the butadiene and/or the catalyst in the water used in the reaction. Such compounds are, for example, organic sulphur compounds, for example crotyl phenyl sulphide and triphenyl thio-phosphite.

The reaction is best carried out at a raised temperature, for example at a temperature within the range 50° to 150° C., preferably 80° to 130° C. The reaction may be conveniently carried out, for example, by adding butadiene, water, solvent and catalyst, and optionally carbon dioxide or sulphur dioxide, to an autoclave, pressurising the autoclave with oxygen and heating the autoclave to the appropriate temperature for the desired time. The time of reaction may be varied according to the degree of conversion desired, and may vary, for example, from 0.5 hour up to 50 hours. The butenediol product may be separated from the reaction mixture, for example by fractional distillation. Unconverted materials may be recycled.

The product consists of a mixture of cis- and trans-2-butene-1, 4-diol with some butene-3, 4-diol. The product may be used as an intermediate in the manufacture of tetrahydrofuran, in the manufacture of polyurethanes, and for conversion to butane-1, 4-diol useful in the manufacture of polyesters.

The invention is illustrated but not limited by the following Examples in which the parts and percentages are by weight except where stated otherwise, and in which the ratio of parts by weight to parts by volume is that of the kilogram to the liter.

EXAMPLES 1 to 3

Butadiene (10 parts by volume), water (5 parts by volume) and the carbon dioxide or sulphur dioxide, catalyst and solvent specified in the following Table were added to an autoclave which was pressurised with oxygen to 3.45 bar (gauge) and heated at 100° for the time shown in the Table. The reaction mixture was found to contain the amount of 2-butene-1, 4-diol specified.

    __________________________________________________________________________                                     Time                                                                           of  Yield of                                                     Solvent and                                                                             Carbon                                                                              Reac-                                                                              2-butene-                                                                           % Conversion of                       Example                                                                             Catalyst and amount (parts                                                                           Dioxide                                                                             tion                                                                               1,4-diol                                                                            butadiene to 2-                       No.  amount (parts)                                                                              by volume)                                                                              (parts)                                                                             (hrs)                                                                              parts                                                                               butene-1,4-diol                       __________________________________________________________________________     1    iron acetylacetonate                                                                     0.25                                                                              acetone                                                                               15                                                         lithium hydroxide                                                                        0.2                                                                               5% sulphur                                                                     dioxide  --   10  0.6  5.8                                                     solution                                                                       in acetone                                                                            0.5                                                   2*   iron acetylacetonate                                                                     0.05                                                                              acetone                                                                               15                                                                               1    20  0.5  4.9                                        lithium hydroxide                                                                        0.05                                                            3*   iron acetylacetonate                                                                     0.01                                                                              acetone                                                                               15                                                                               --   20  0.3  2.9                                        lithium hydroxide                                                                        0.01                                                            __________________________________________________________________________      *nitrogen at 3.45 bar (gauge) was also supplied to the autoclave          

I claim:
 1. A process for the manufacture of 2-butene-1, 4-diol which comprises reacting butadiene with water and oxygen in the presence of an iron catalyst.
 2. A process according to claim 1 which is carried out in the presence of carbon dioxide or sulphur dioxide.
 3. A process according to claim 2 in which the amount of carbon dioxide or sulphur dioxide is 0.01 to 0.5 mols carbon dioxide or sulphur dioxide per mole of butadiene.
 4. A process according to claim 1 in which at least 1 mole of water is used per mole of butadiene.
 5. A process according to claim 1 in which the catalyst is an inorganic salt or an organic acid salt.
 6. A process according to claim 1 in which lithium hydroxide is present.
 7. A process according to claim 1 which is carried out in the liquid phase in the presence of a solvent.
 8. A process according to claim 1 which is carried out at a temperature in the range 50° to 150° C.
 9. A process according to claim 1 in which the process is carried out in the liquid phase at a temperature in the range 50° to 150° C. in a solvent selected from the group consisting of lower aliphatic alcohols, lower aliphatic ketones and lower alkyl cyanides in the presence of lithium hydroxide and, as catalyst, of an iron halide or iron salt of an aliphatic carboxylic acid containing up to 20 carbon atoms.
 10. A process according to claim 9 in which carbon dioxide or sulphur dioxide is also present. 